EP0904257A1 - Engrais a base de nitrate de calcium - Google Patents

Engrais a base de nitrate de calcium

Info

Publication number
EP0904257A1
EP0904257A1 EP97922215A EP97922215A EP0904257A1 EP 0904257 A1 EP0904257 A1 EP 0904257A1 EP 97922215 A EP97922215 A EP 97922215A EP 97922215 A EP97922215 A EP 97922215A EP 0904257 A1 EP0904257 A1 EP 0904257A1
Authority
EP
European Patent Office
Prior art keywords
fertilizer
weight
calcium nitrate
gypsum
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP97922215A
Other languages
German (de)
English (en)
Other versions
EP0904257B1 (fr
Inventor
Torstein Obrestad
Johanne R DSVIK
Torbj rn LEGARD
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Norsk Hydro ASA
Original Assignee
Norsk Hydro ASA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Norsk Hydro ASA filed Critical Norsk Hydro ASA
Publication of EP0904257A1 publication Critical patent/EP0904257A1/fr
Application granted granted Critical
Publication of EP0904257B1 publication Critical patent/EP0904257B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05CNITROGENOUS FERTILISERS
    • C05C5/00Fertilisers containing other nitrates
    • C05C5/04Fertilisers containing other nitrates containing calcium nitrate

Definitions

  • the present invention relates to calcium nitrate based fertilizers containing sulphur and a process for making such fertilizers.
  • Calcium nitrate is widely used within horticulture and as a dry product on open fields.
  • the latter normally contains 75-81 weight% Ca(NO 3 ) 2 , 5-9 weight% NH 4 NO 3 and 12-14 weight% water of crystallization.
  • This type is usually called NH-CN (Norsk Hydro Calcium Nitrate).
  • CN will be used for both these types of fertilizer.
  • the main object of the present invention was to arrive at a homogeneous CN-based fertilizer containing sulphur and optionally magnesium, selenium, cobalt and micronut ⁇ ents Another object was to arrive at a cost effective continuous process for making homogeneous sulphur containing CN-based fertilizers which could be par- ticulated.
  • a further object was to arrive at a process for making homogeneous sulphur containing CN-based fertilizers containing magnesium and optionally selenium, cobalt and micronutrients.
  • gypsum consumes calcium nitrate and the melt loses its ability to solidify due to less power to tie up water of crystallization. Accordingly, the two S-sources were found to be too difficult to apply in CN-based fertilizers.
  • Gypsum (CaSO 4 1/2 H 2 O) was expected to not react with CN melt and should therefore constitute a cheap S-source. Even though gypsum is not water soluble, several agronomical examinations have shown that gypsum is readily available to plants. Different gypsum sources can be utilized, such as dead burned gypsum and gypsum with hydrate water up to dihydrate, the hemi hydrate form is however preferred.
  • Kieserite (MgSO 4 H 2 O) is both a Mg- and S-source which is considered to be water soluble. By mixing this salt into a CN melt the following reaction was found to take place:
  • reaction no. 3 did not take place at a significant rate.
  • kieserite was thoroughly mixed into CN melt for several minutes it was confirmed that said reaction did not result in solidification problems.
  • the investigations also showed that reaction 3 indeed did take place at the surface of each kieserite crystal, but the gypsum formed a thin coating that protected the crystals from further attack by the CN melt.
  • solid gypsum and/or a slow reacting sulphate mineral could be mixed with melted calcium nitrate fertilizer at a temperature of 90-110°C and kept at this temperature for 3-15 minutes and subsequently particulated at a temperature of 80-110°C.
  • the particulation by prilling should be performed at 95-110°C and the granulation at 90-110°C.
  • Microamounts of Co and/or Se and/or micronutrients like Mn, Cu, B, and Zn could be added as solutions of their salts to the mixture prior to particulation.
  • One preferred method comprises mixing 4-23 weight% gypsum, based on the total composition, with a melted calcium nitrate fertilizer at 103-106°C during stirring and keeping the mixture at this temperature for 5-10 minutes and then particulate the thus formed slurry.
  • Another preferred method comprises mixing 4-23 weight% kieserite during stirring with a melted calcium nitrate fertilizer for 6-12 minutes and subsequently particulate the thus formed slurry.
  • Fertilizers according to the invention comprise a homogeneous composition of a calcium nitrate fertilizer and gypsum and/or a slow reacting sulphate mineral comprising 0.1-5.0 weight% SO 4 -S, 14-19 weight% water soluble calcium and 16-21 weight% total calcium and 0-3.0 weight% water soluble magnesium
  • said new fertilizer contains 1.0-3.0 weight% SO 4 -S.
  • the preferred content of magnesium is 0.1-4.0 weight%.
  • This example relates to formation of prilled homogeneous CN-based fertilizer by mixing 12 weight% kieserite crystals into NH-CN melt at 105°C during stirring at this temperature for about 10 minutes and then spraying the slurry through a nozzle. The formed droplets solidified as they fell through cooling air.
  • the product thus formed had a homogeneous composition and had the following analysis:
  • This example shows drum granulation of a homogeneous CN-based fertilizer.
  • 7 weight% kieserite crystals were mixed into 93 weight% NH-CN melt at 105°C and stirred for about 6 minutes.
  • the slurry was then sprayed into a drum containing fines from example 1.
  • Hard homogeneous granules were formed with the following composition:
  • This example shows granulation of homogeneous CN-based fertilizer containing sulphur 11 5 we ⁇ ght% calcium sulphate hemi hydrate (22 1 %S) was mixed with 88 5 we ⁇ ght% NH-CN melt at about 105°C and stirred for about 5 minutes and subsequently sprayed into a rotating drum containing NH-CN fines
  • the thereby formed product had the following analysis
  • This example shows preparation of homogeneous CN-based fertilizer containing sulphur and magnesium and in addition selenium 7 we ⁇ ght% kieserite and some droplets of a 25 we ⁇ ght% Na 2 SeO 4 solution were mixed into a NH-CN melt at about 105°C and stirred for about 5 minutes The melt was solidified as in example 2
  • the formed product had the following analysis
  • This example shows preparation of homogeneous CN-based fertilizer containing both sulphur and magnesium 4 we ⁇ ght% gypsum (calcium sulphate hemi hydrate) and 6 we ⁇ ght% kieserite were thoroughly mixed into 90 we ⁇ ght% of NH-CN melt at about 105°C for about 4 minutes The thereby formed slurry was then sprayed into a granulating drum containing fines Hard, homogeneous granules were formed with the following composition
  • gypsum is a cheaper sulphur source than kieserite and that the product is somewhat less hygroscopic than a product using only kieserite as sulphur and magnesium source.
  • Mg (w.s) 0-4.0 weight% preferably: 0-2.3
  • Ca (w.s) 14-19 weight% preferably: 16-19
  • fertilizers of the above type can contain microamounts of cobalt and selenium, and the usual fertilizer micronutrients like manganese, copper zinc, boron etc.
  • a new type of fertilizer being a homogeneous fertilizer based on calcium nitrate and containing the required amount of sulphur.
  • Said new fertilizer may also contain magnesium and microamounts of Se and Co and micronutrients like Mn, Cu, B, Zn etc.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Fertilizers (AREA)
  • Micro-Organisms Or Cultivation Processes Thereof (AREA)
  • Catalysts (AREA)
  • Cosmetics (AREA)

Abstract

Cette invention concerne des engrais homogènes à base de nitrate de calcium et contenant du soufre, ainsi qu'un procédé de préparation de ces engrais. Du gypse solide et/ou un minéral à base de sulfate et à réaction lente sont mélangés à une température de 90 à 110 °C avec un engrais à base de nitrate de calcium fondu. Le mélange est maintenu à cette température pendant une durée de 3 à 15 minutes, puis mis sous forme de particules à une température de 80 à 110 °C. La mise sous forme de particules par grelonage se fait à une température allant de 95 à 110 °C, tandis que la mise sous forme de particules par granulation se fait à une température allant de 90 à 110 °C. Cet engrais se présente sous forme d'une composition homogène contenant un nitrate de calcium ainsi qu'un gypse et/ou un minéral à base de sulfate et à réaction lente. Cette composition comprend de 0,1 à 5,0 % en poids de SO4-S, de 14 à 19 % en poids de calcium soluble dans l'eau, un total de 16 à 21 % en poids de calcium, et de 0 à 3,0 % en poids de magnésium soluble dans l'eau. Cet engrais peut également comprendre des micro-quantités de Se et/ou de Co, et/ou des micro-éléments nutritifs tels que du Mn, du Cu, du B et du Zn.
EP97922215A 1996-05-24 1997-05-14 Engrais a base de nitrate de calcium Expired - Lifetime EP0904257B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
NO962119 1996-05-24
NO962119A NO305939B1 (no) 1996-05-24 1996-05-24 Metode for fremstilling av kalsiumnitratbasert gjoedsel inneholdende svovel, samt slik gjoedsel
PCT/NO1997/000126 WO1997045382A1 (fr) 1996-05-24 1997-05-14 Engrais a base de nitrate de calcium

Publications (2)

Publication Number Publication Date
EP0904257A1 true EP0904257A1 (fr) 1999-03-31
EP0904257B1 EP0904257B1 (fr) 2000-08-09

Family

ID=19899417

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97922215A Expired - Lifetime EP0904257B1 (fr) 1996-05-24 1997-05-14 Engrais a base de nitrate de calcium

Country Status (13)

Country Link
US (1) US6171358B1 (fr)
EP (1) EP0904257B1 (fr)
AT (1) ATE195309T1 (fr)
AU (1) AU2794697A (fr)
CZ (1) CZ292236B6 (fr)
DE (1) DE69702760D1 (fr)
IL (1) IL127203A (fr)
NO (1) NO305939B1 (fr)
PL (1) PL185085B1 (fr)
PT (1) PT904257E (fr)
RO (1) RO117909B1 (fr)
RU (1) RU2162073C2 (fr)
WO (1) WO1997045382A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6319156B1 (en) * 1999-12-13 2001-11-20 John Marshall Biodegradable golf tee
KR20020008486A (ko) * 2000-07-20 2002-01-31 강준구 농업용 비료
PL200842B1 (pl) * 2004-09-16 2009-02-27 Adam Nawrocki Sposób wytwarzania nawozu zawierającego azotan wapnia
KR20120084299A (ko) * 2009-10-05 2012-07-27 스페셜티 퍼틸라이저 프로덕츠 엘엘씨 중합체 보조제로 강화된 비료 제품
CN103254002A (zh) * 2012-02-21 2013-08-21 吴兴国 酵素麦饭石富硒生物有机肥
ES2899829T3 (es) * 2016-04-14 2022-03-14 Yara Int Asa Composición en partículas de nitrato de calcio para fertirrigación, que comprende micronutrientes a base de nitrato y método para la fabricación de la misma
CA2968257C (fr) * 2017-05-24 2022-05-24 Inotel Inc. Fertilisant au potassium et magnesium

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE203085C (fr) *
DE397937C (de) * 1920-03-09 1924-07-03 Hoechst Ag Verfahren zur Herstellung eines gut streubaren, nicht wasseranziehenden Kali-Stickstoffmischduengers
BE754561A (fr) 1969-08-09 1971-02-08 Badishe Anilin & Soda Fabrik Sel double de nitrate de calcium et d'uree se pretant bien a l'epandageen granules et au stockage
AT306754B (de) 1971-03-29 1973-04-25 Chemie Linz Ag Überwiegend aus freiem Ammonnitrat bestehendes, granuliertes, gespritztes oder geprilltes Düngemittel
JPS5327564A (en) 1976-08-25 1978-03-14 Kawasaki Heavy Ind Ltd Calcium nitrate fertilizer difficult to deliquesce and process for producing same
JPS5485957A (en) 1977-12-19 1979-07-09 Shimohiro Shiyuku Production of composite fertilizer
US5698002A (en) * 1994-11-21 1997-12-16 Lesco Inc. Controlled release fertilizers utilizing an epoxy polymer primer coat and methods of production

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9745382A1 *

Also Published As

Publication number Publication date
NO305939B1 (no) 1999-08-23
CZ292236B6 (cs) 2003-08-13
NO962119L (no) 1997-11-25
PL185085B1 (pl) 2003-02-28
PL330231A1 (en) 1999-05-10
AU2794697A (en) 1998-01-05
US6171358B1 (en) 2001-01-09
ATE195309T1 (de) 2000-08-15
NO962119D0 (no) 1996-05-24
RU2162073C2 (ru) 2001-01-20
WO1997045382A1 (fr) 1997-12-04
IL127203A (en) 2001-09-13
PT904257E (pt) 2001-01-31
CZ375998A3 (cs) 1999-04-14
EP0904257B1 (fr) 2000-08-09
IL127203A0 (en) 1999-09-22
RO117909B1 (ro) 2002-09-30
DE69702760D1 (de) 2000-09-14

Similar Documents

Publication Publication Date Title
CN110198779B (zh) 杂卤石制粒方法
FI105807B (fi) Menetelmä seoslannoitterakeiden valmistamiseksi
US4175943A (en) Water-soluble fertilizers
US11655196B2 (en) Granules of polyhalite and urea
AU2007251520C1 (en) Fertilizer granules and manufacturing process thereof
US10988419B2 (en) Binders for the granulation of fertilizers
US6171358B1 (en) Calcium nitrate based fertilizer
CA1120282A (fr) Methode de preparation d'un engrais granulaire npk, et engrais granulaires npk ainsi obtenus
AU2002339757B2 (en) Method for production of nitrate-containing products from undercooling melts
PL184223B1 (pl) Nawóz azotowo-potasowy i sposób wytwarzania nawozu azotowo-potasowego
US4256479A (en) Granulation of fertilizer borate
RU2812767C2 (ru) Композиция в форме частиц, включающая нитрат кальция и молибден, и способ ее получения
CN113423679B (zh) 包含硝酸钙和钼的颗粒组合物及其制造方法
DK171130B1 (da) Indkapslet gødningsmiddel med neutraliserende evne
JPH0114197B2 (fr)
EP3626696A1 (fr) Compositions comprenant des thiosulfates, polysulfures solides et/ou des (bi)sulfites et procédés pour leur préparation
NZ286023A (en) Production of nutrient-coated urea fertilizer granules by tumbling coating with minimal water present
HU192754B (en) Process for producing suspension containing nitrogen, calcium and if desired potassium
CS235112B1 (cs) Způsob úpravy granulovaných hnojiv
JPS62235283A (ja) 尿素を結合媒体にした含鉄配合肥料の製造方法
PL134740B1 (en) Method of obtaining granulated ammonium nitrate

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19981228

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT DE DK ES FI FR GB GR IE NL PT SE

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

17Q First examination report despatched

Effective date: 19990514

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

RIN1 Information on inventor provided before grant (corrected)

Inventor name: LEGARD, TORBJOERN

Inventor name: ROEDSVIK, JOHANNE

Inventor name: OBRESTAD, TORSTEIN

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT DE DK ES FI FR GB GR IE NL PT SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20000809

Ref country code: FR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20000809

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20000809

Ref country code: ES

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 20000809

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20000809

REF Corresponds to:

Ref document number: 195309

Country of ref document: AT

Date of ref document: 20000815

Kind code of ref document: T

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 69702760

Country of ref document: DE

Date of ref document: 20000914

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20001109

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20001109

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20001110

Ref country code: DE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20001110

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
EN Fr: translation not filed
REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 20001026

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010514

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010514

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20010514

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PT

Payment date: 20160511

Year of fee payment: 20

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20170523